U.S. patent application number 14/575397 was filed with the patent office on 2015-06-25 for processing-friendly dianhydride hardener for epoxy resin systems based on 5,5'-carbonylbis(isobenzofuran-1,3-dione).
This patent application is currently assigned to EVONIK INDUSTRIES AG. The applicant listed for this patent is Manfred Neumann, Benjamin WILLY. Invention is credited to Manfred Neumann, Benjamin WILLY.
Application Number | 20150175740 14/575397 |
Document ID | / |
Family ID | 52102475 |
Filed Date | 2015-06-25 |
United States Patent
Application |
20150175740 |
Kind Code |
A1 |
WILLY; Benjamin ; et
al. |
June 25, 2015 |
PROCESSING-FRIENDLY DIANHYDRIDE HARDENER FOR EPOXY RESIN SYSTEMS
BASED ON 5,5'-CARBONYLBIS(ISOBENZOFURAN-1,3-DIONE)
Abstract
The present invention provides a composition comprising
5,5'-carbonylbis(isobenzofuran-1,3-dione),
3,3',4,4'-benzophenonetetracarboxylic acid and at least one
monoanhydride compound selected from the group consisting of
methylhexahydroisobenzofuran-1,3-dione,
5-methyl-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione,
5-methyl-3a,4,7,7a-tetrahydroisobenzofuran-1,3-dione,
3-methylfuran-2,5-dione,
3,3,4,4,5,5-hexafluorodihydro-2H-pyran-2,6(3H)-dione and
3,3-dimethyldihydrofuran-2,5-dione. The invention also provides a
hardener system for an epoxy resin, said hardener system comprising
said composition. The invention also provides a method for
hardening an epoxy resin employing the inventive composition.
Inventors: |
WILLY; Benjamin;
(Duesseldorf, DE) ; Neumann; Manfred; (Marl,
DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
WILLY; Benjamin
Neumann; Manfred |
Duesseldorf
Marl |
|
DE
DE |
|
|
Assignee: |
EVONIK INDUSTRIES AG
Essen
DE
|
Family ID: |
52102475 |
Appl. No.: |
14/575397 |
Filed: |
December 18, 2014 |
Current U.S.
Class: |
528/361 ;
252/183.11 |
Current CPC
Class: |
C08G 59/4284 20130101;
C08G 59/4007 20130101; C08G 59/4223 20130101 |
International
Class: |
C08G 59/42 20060101
C08G059/42; C08G 59/40 20060101 C08G059/40 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 19, 2013 |
DE |
102013226601.4 |
Claims
1. A composition comprising:
5,5'-carbonylbis(isobenzofuran-1,3-dione);
3,3',4,4'-benzophenonetetracarboxylic acid; and a monoanhydride
compound selected from the group consisting of
methylhexahydroisobenzofuran-1,3-dione,
5-methyl-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione,
5-methyl-3a,4,7,7a-tetrahydroisobenzofuran-1,3-dione,
3-methylfuran-2,5-dione,
3,3,4,4,5,5-hexafluorodihydro-2H-pyran-2,6(3H)-dione and
3,3-dimethyldihydrofuran-2,5-dione.
2. The composition according to claim 1, wherein the monoanhydride
compound is selected from the group consisting of
methylhexahydroisobenzofuran-1,3-dione,
5-methyl-3a,4,7,7a-tetrahydroisobenzofuran-1,3-dione and
5-methyl-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione.
3. The composition according to claim 1, wherein the monoanhydride
compound is at least one of
5-methyl-3a,4,7,7a-tetrahydroisobenzofuran-1,3-dione and
5-methyl-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione.
4. The composition according to claim 1, wherein the monoanhydride
compound is
5-methyl-3a,4,7,7a-tetrahydroisobenzofuran-1,3-dione.
5. The composition according to claim 1, wherein a ratio of the
mass of 5,5'-carbonylbis(isobenzofuran-1,3-dione) in the
composition to the sum total of the mass of
methylhexahydroisobenzofuran-1,3-dione, the mass of
5-methyl-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione,
the mass of 5-methyl-3a,4,7,7a-tetrahydroisobenzofuran-1,3-dione,
the mass of 3-methylfuran-2,5-dione, the mass of
3,3,4,4,5,5-hexafluorodihydro-2H-pyran-2,6(3H)-dione and the mass
of 3,3-dimethyldihydrofuran-2,5-dione in the composition is 1:0.35
to 1:2.05.
6. The composition according to claim 1, wherein the mass of
3,3',4,4'-benzophenonetetracarboxylic acid in the composition is
from 0.01 to 17.6% of the sum total of the mass of
5,5'-carbonylbis(isobenzofuran-1,3-dione), the mass of
methylhexahydroisobenzofuran-1,3-dione, the mass of
5-methyl-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione,
the mass of 5-methyl-3a,4,7,7a-tetrahydroisobenzofuran-1,3-dione,
the mass of 3-methylfuran-2,5-dione, the mass of
3,3,4,4,5,5-hexafluorodihydro-2H-pyran-2,6(3H)-dione and the mass
of 3,3-dimethyldihydrofuran-2,5-dione in the composition.
7. A hardener system for epoxy resins, comprising the composition
according to claim 1, wherein a proportion by mass of the
composition of claim 1 is from 10% to 100% by mass, based on the
total mass of the hardener system.
8. The hardener system according to claim 7, wherein the hardener
system is free of any amine compound.
9. The hardner system according to claim 7, wherein the hardner
system is free of any metal salt.
10. The hardner system according to claim 8, wherein the hardner
system is free of any metal salt.
11. A method for hardening an epoxy resin, comprising mixing the
hardener system according to claim 7 with the epoxy resin to be
hardened.
12. The method for hardening an epoxy resin according to claim 11,
wherein a combination of components comprising
5,5'-carbonylbis(isobenzofuran-1,3-dione) and a monoanhydride
compound is added to the epoxy resin to obtain a first resin
mixture; 3,3',4,4'-benzophenonetetracarboxylic acid is added to the
first resin mixture to obtain a final epoxy resin mixture; and the
final epoxy resin mixture is hardened at a temperature of at least
25.degree. C.; wherein the monoanhydride compound is selected from
the group consisting of methylhexahydroisobenzofuran-1,3-dione,
5-methyl-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione,
5-methyl-3a,4,7,7a-tetrahydroisobenzofuran-1,3-dione,
3-methylfuran-2,5-dione,
3,3,4,4,5,5-hexafluorodihydro-2H-pyran-2,6(3H)-dione and
3,3-dimethyldihydrofuran-2,5-dione.
13. The method for hardening an epoxy resin according to claim 12,
wherein the hardening temperature is from 25.degree. C. to below
the melting temperature of
5,5'-carbonylbis(isobenzofuran-1,3-dione).
14. The method for hardening an epoxy resin according to claim 11,
wherein a hardener mixture comprising
5,5'-carbonylbis(isobenzofuran-1,3-dione),
3,3',4,4'-benzophenonetetracarboxylic acid and a monoanhydride
compound is prepared, an epoxy resin is added to the hardener
mixture to obtain an epoxy resin hardener mixture; and the epoxy
resin hardener mixture is hardened at a temperature of at least
25.degree. C., wherein the monoanhydride compound is selected from
the group consisting of methylhexahydroisobenzofuran-1,3-dione,
5-methyl-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione,
5-methyl-3a,4,7,7a-tetrahydroisobenzofuran-1,3-dione,
3-methylfuran-2,5-dione,
3,3,4,4,5,5-hexafluorodihydro-2H-pyran-2,6(3H)-dione and
3,3-dimethyldihydrofuran-2,5-dione.
15. The method for hardening an epoxy resin according to claim 14,
wherein the hardening temperature is from 25.degree. C. to below
the melting temperature of
5,5'-carbonylbis(isobenzofuran-1,3-dione).
16. An epoxy resin system, comprising: an epoxy resin; and a
hardener system according to claim 7.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to German Application No.
102013226601.4 filed Dec. 19, 2013, the disclosure of which is
incorporated herein by reference in its entirety.
BACKGROUND OF THE INVENTION
[0002] The present invention relates to a composition
comprising
[0003] a. 5,5'-carbonylbis(isobenzofuran-1,3-dione);
[0004] b. 3,3',4,4'-benzophenonetetracarboxylic acid; and
[0005] c. at least one monoanhydride compound selected from the
group consisting of methylhexahydroisobenzofuran-1,3-dione,
5-methyl-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione,
5-methyl-3a,4,7,7a-tetrahydroisobenzofuran-1,3-dione,
3-methylfuran-2,5-dione,
3,3,4,4,5,5-hexafluorodihydro-2H-pyran-2,6(3H)-dione,
3,3-dimethyldihydrofuran-2,5-dione.
[0006] The invention also relates to a hardener system for epoxy
resins, said hardener system comprising said composition. The
invention also relates to the use of said hardener system for
hardening of epoxy resins and to corresponding methods.
[0007] Epoxy resins are one of the most versatile polymeric
materials. They find uses, for example, as coatings, adhesives,
casting resin compounds, moulding compounds, as embedding compounds
for encasing electronic components, as laminates and base material
for printed circuits, and as matrix resins for fibre-reinforced
plastics.
[0008] The conversion of monomeric or polymeric epoxy resins to
polymeric substances requires co-reactants, which are referred to
as hardeners or hardening agents. According to the hardener type,
the hardening reaction is effected at temperatures around room
temperature or low temperatures (called "cold curing") or at
elevated temperatures (called "warm or hot curing"). For hardening
of epoxy resins at low temperatures for industrial applications,
predominantly only aliphatic primary or secondary amines and
polyamines are used; less commonly used, in contrast, are
polythiols or specific salts.
[0009] All unmodified amines are alkaline to strongly alkaline.
Liquid amines, especially the aliphatic and cycloaliphatic amines,
can cause skin damage extending as far as chemical burns. Another
disadvantage is the high volatility of the liquid amines. A great
disadvantage of the cold curing of epoxy resins with the
abovementioned hardening agents is the low thermal resistance and
chemical resistance of the resultant products. To increase the
thermal stability, solvent stability and chemical stability, one is
forced to harden epoxy resins at elevated temperatures in a hot
curing operation with aromatic or cycloaliphatic amines, carboxylic
anhydrides, polyphenols, or with latent hardeners.
[0010] However, there is a demand for epoxy resin hardener systems
which can harden at minimum temperature and give rise to products
having an elevated thermal stability, chemical stability and
solvent stability. Potential applications for these are, for
example, adhesives, matrix resins for fibre composites and repair
resins for components where the employment of high temperatures is
not an option. Further applications are casting resin and embedding
compounds, specifically for encasing of large electronic
components, where the hardening can proceed at low temperature,
with low exothermicity and consequently with a considerable energy
saving, a further advantage being that products with reduced
internal stress are the result.
[0011] It is conventionally known that the hardening of epoxy
resins, especially in the case of bisphenol A resins, with cyclic
dicarboxylic anhydrides and tetracarboxylic bisanhydrides requires
hardening temperatures of at least 120-150.degree. C., in which
case hardening times of several hours are required; see
Houben-Weyl, Methoden der Organischen Chemie [Methods of Organic
Chemistry], volume E20, Makromolekulare Stoffe [Macromolecular
Substances], Georg Thieme Verlag Stuttgart, 1987, page 1959. Even
at these temperatures, the crosslinking reaction is still so slow
that it is generally not possible to avoid using accelerators. It
is advantageous, however, that the hardening with anhydrides
proceeds with lower exothermicity compared to hardening with
amines. The hardened products have good electrical insulation
properties and good thermal stability.
[0012] U.S. Pat. No. 4,002,599 describes hardening of epoxy resins
with cyclic acid anhydrides at low temperatures. However, only
systems based on polyglycidyl-substituted aminophenols are
described.
[0013] DE 2837726 describes epoxy resin compositions composed of at
least one epoxy resin and a hardening agent, said hardening agent
comprising 2,3,3',4'-diphenyltetracarboxylic anhydride. The
anhydride first has to be dissolved before hardening can be
effected; in some cases, the mixture is even cooled down again.
This can lead to problems; more particularly, the hardening agent
can separate out.
[0014] An additional disadvantage of conventional methods is the
need to utilize a catalyst for hardening and therefore to be
reliant particularly on the use of amines. The above-discussed
irritant effect of the aliphatic and cycloaliphatic amines can be
alleviated somewhat by use of aromatic amines as catalysts, as
described in U.S. Pat. No. 3,989,573, where
2-ethyl-4-methylimidazole was used. However, it would be even more
desirable to be able to entirely dispense with the use of such
catalysts and nevertheless to be able to obtain such polymerization
rates as would enable the use of the hardener systems.
[0015] In addition, there is the need to have available a
user-friendly hardener system. Thus, many hardener systems which
are composed of a dianhydride compound and a monoanhydride compound
have the problematic property of being in the form of a
fine-dusting powder over a wide mixing range of the two components,
which makes them difficult to process and makes the addition of
solvents unavoidable. Such an addition of solvents again prevents
formulation of the desired hardener system in a high concentration,
i.e. with a minimum level of other substances. For use as a
hardener system, however, it is precisely such high concentrations
that should not be present in powder form that are desired.
Furthermore, it is disadvantageous when the solid is present in
excessively dilute form, since settling of the solid then sets in
within a few hours, which leads to unwanted inhomogeneities in the
composition.
[0016] It is therefore also desirable to obtain a non-dusting
formulation which is stable and storable over a wide mixing
range.
[0017] It is therefore an object of the present invention to
provide an improved hardener system for the hardening of epoxy
resins. This hardener system shall be easy to process and, after
hardening, lead to resin systems--even without the use of the
conventional catalysts mentioned--with a good, lasting heat
distortion resistance. At the same time, the system shall allow
good formulatability over a wide concentration range of the
dianhydride compound and monoanhydride compound, and at the same
time be storable with respect to homogeneity. Finally, the use of
catalysts composed of amine compounds or metal salts shall also be
avoided, and a good polymerization rate shall nevertheless be
achievable.
SUMMARY OF THE INVENTION
[0018] These and other objects have been achieved according to the
present invention, the first embodiment of which includes a
composition comprising:
[0019] 5,5'-carbonylbis(isobenzofuran-1,3-dione);
[0020] 3,3',4,4'-benzophenonetetracarboxylic acid; and
[0021] a monoanhydride compound selected from the group consisting
of methylhexahydroisobenzofuran-1,3-dione,
5-methyl-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione,
5-methyl-3a,4,7,7a-tetrahydroisobenzofuran-1,3-dione,
3-methylfuran-2,5-dione,
3,3,4,4,5,5-hexafluorodihydro-2H-pyran-2,6(3H)-dione and
3,3-dimethyldihydrofuran-2,5-dione.
[0022] In another embodiment, the present invention includes a
hardener system for epoxy resins, comprising the composition
according to the first embodiment, wherein a proportion by mass of
the composition is from 10% to 100% by mass, based on the total
mass of the hardener system.
[0023] In a further embodiment, the present invention provides a
method for hardening an epoxy resin, comprising mixing the hardener
system according the invention with the epoxy resin to be
hardened.
[0024] The foregoing paragraphs have been provided by way of
general introduction, and are not intended to limit the scope of
the following claims. The described embodiments, together with
further advantages, will be best understood by reference to the
following detailed description.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0025] In the following description, the words "a" and "an" and the
like carry the meaning of "one or more." The phrases "selected from
the group consisting of," "chosen from," and the like include
mixtures of the specified materials. Terms such as "contain(s)" and
the like are open terms meaning `including at least` unless
otherwise specifically noted. Where a numerical limit or range is
stated, the endpoints are included. Also, all values and subranges
within a numerical limit or range are specifically included as if
explicitly written out.
[0026] The inventors have surprisingly and unexpectedly found that
addition of 3,3',4,4'-benzophenonetetracarboxylic acid ("BTA"
hereinafter) to the hardener to accelerate the polymerization
achieves the objects of the invention as described above.
[0027] Thus in a first embodiment the present invention
provides
[0028] 1. a composition comprising
[0029] a. 5,5'-carbonylbis(isobenzofuran-1,3-dione) ("s-BTDA"
hereinafter);
[0030] b. 3,3',4,4'-benzophenonetetracarboxylic acid; and
[0031] c. at least one monoanhydride compound selected from the
group consisting of methylhexahydroisobenzofuran-1,3-dione
("MHHPSA" hereinafter),
5-methyl-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione
("MNA" hereinafter),
5-methyl-3a,4,7,7a-tetrahydroisobenzofuran-1,3-dione ("MTHPA"
hereinafter), 3-methylfuran-2,5-dione ("MFD" hereinafter),
3,3,4,4,5,5-hexafluorodihydro-2H-pyran-2,6(3H)-dione ("HFDPA"
hereinafter), 3,3-dimethyldihydrofuran-2,5-dione ("DMDF"
hereinafter").
[0032] In a further embodiment of the present invention, the
composition according to the first embodiment is characterized in
that the monoanhydride compound is selected from the group
consisting of MHHPSA, MTHPA, MNA; preferably selected from the
group consisting of MTHPA, MNA and in one preferred aspect the
monoanhydride compound is MTHPA.
[0033] In a further embodiment of the present invention, the
composition according to the above description is characterized in
that the ratio of the mass of s-BTDA in the composition to the sum
total of the mass of MHHPSA, the mass of MNA, the mass of MTHPA,
the mass of MFD, the mass of HFDPA, the mass of DMDF in the
composition is 1:0.35 to 1:2.05, preferably 1:0.361 to 1:2.010,
more preferably 1:0.619 to 1:1.237.
[0034] In a further embodiment of the present invention, the
composition is characterized in that the mass of BTA in the
composition is 0.01 to 17.6% of the sum total of the mass of
s-BTDA, the mass of MHHPSA, the mass of MNA, the mass of MTHPA, the
mass of MFD, the mass of HFDPA and the mass of DMDF in the
composition.
[0035] The present invention further provides a hardener system for
epoxy resins, comprising the composition according to the above
description in a proportion by mass of 0.10 to 1.0, based on the
total mass of the hardener system. According to the invention the
hardener system for epoxy resins may not include any amine compound
and further a metal salt may not be included.
[0036] In a further embodiment, the present invention relates to an
epoxy resin system comprising an epoxy resin and at least one
hardener system according to the above description.
[0037] The present invention provides a composition consisting
of
[0038] a. s-BTDA;
[0039] b. BTA; and
[0040] c. at least one monoanhydride compound selected from the
group consisting of MHHPSA, MNA, MTHPA, MFD, HFDPA, DMDF. In this
composition the ratio of the mass of s-BTDA in the composition to
the sum total of the mass of MHHPSA, the mass of MNA, the mass of
MTHPA, the mass of MFD, the mass of HFDPA and the mass of DMDF in
the composition is 1:0.35 to 1:2.05, preferably 1:0.361 to 1:2.010,
more preferably 1:0.619 to 1:1.237. Further the mass of BTA in the
composition is 0.01 to 17.6% of the sum total of the mass of
s-BTDA, the mass of MHHPSA, the mass of MNA, the mass of MTHPA, the
mass of MFD, the mass of HFDPA, the mass of DMDF in the
composition.
[0041] In a further embodiment, the present invention provides a
hardener system for epoxy resins, comprising the composition
described in the previous paragraph in a proportion by mass of 0.10
to 1.0, based on the total mass of the hardener system. This system
may not include any amine compound and may not include any metal
salt.
[0042] The present invention further provides a method for
hardening epoxy resins, wherein
[0043] a. in a first step at least one epoxy resin is mixed
with
[0044] i. s-BTDA; and
[0045] ii. at least one monoanhydride compound selected from the
group consisting of MHHPSA, MNA, MTHPA, MFD, HFDPA, DMDF;
[0046] b. in a second step BTA is added; and
[0047] c. in a third step the epoxy resin is hardened at a
temperature of at least 25.degree. C.
[0048] In another method embodiment the present invention provides
a method for hardening epoxy resins, wherein
[0049] a. in a first step
[0050] i. s-BTDA; and
[0051] ii. BTA; and
[0052] iii. at least one monoanhydride compound selected from the
group consisting of MHHPSA, MNA, MTHPA, MFD, HFDPA, DMDF are
mixed;
[0053] b. in a second step at least one epoxy resin is added;
and
[0054] c. in a third step the epoxy resin is hardened at a
temperature of at least 25.degree. C.
[0055] In a further aspects of these embodiments the hardening of
the epoxy resin is effected in the range from 25.degree. C. to
below the melting temperature of the s-BTDA, which is within the
range of 230.degree. C. to 250.degree. C.
[0056] Thus, in the first embodiment the present invention provides
a composition comprising:
[0057] 5,5'-carbonylbis(isobenzofuran-1,3-dione);
[0058] 3,3',4,4'-benzophenonetetracarboxylic acid; and
[0059] a monoanhydride compound selected from the group consisting
of methylhexahydroisobenzofuran-1,3-dione,
5-methyl-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione,
5-methyl-3a,4,7,7a-tetrahydroisobenzofuran-1,3-dione,
3-methylfuran-2,5-dione,
3,3,4,4,5,5-hexafluorodihydro-2H-pyran-2,6(3H)-dione and
3,3-dimethyldihydrofuran-2,5-dione.
[0060] More particularly, the monoanhydride compound in the
inventive composition is selected from the group consisting of
MHHPSA, MTHPA, MNA. More preferably, the monoanhydride compound in
the inventive composition is selected from the group consisting of
MTHPA, MNA. Even more preferably, the monoanhydride compound in the
inventive composition is MTHPA.
[0061] The structural formulae of the respective compounds are as
follows:
##STR00001##
[0062] As is apparent from the examples, it is a feature of the
inventive composition that it polymerizes more quickly because of
the presence of BTA and may thus also be used as a hardener for
epoxy resins. In this way, it is possible to dispense with the use
of highly corrosive amine compounds as catalysts. Equally, this
also makes it possible to dispense with the use of metal salts for
catalysis, which is advantageous particularly in industrial scale
plants, since metal salts are deposited therein and typically lead
to corrosion of plant components.
[0063] In an advantageous embodiment of the present invention, the
ratio of the mass of s-BTDA in the inventive composition to the sum
total of the mass of MHHPSA, the mass of MNA, the mass of MTHPA,
the mass of MFD, the mass of HFDPA and the mass of DMDF in the
inventive composition is 1:0.35 to 1:2.05, preferably 1:0.361 to
1:2.010, more preferably 1:0.619 to 1:1.237.
[0064] It will be appreciated that the expression "sum total of the
mass of MHHPSA, the mass of MNA, the mass of MTHPA, the mass of
MFD, the mass of HFDPA, the mass of DMDF", when it is abbreviated
to ".SIGMA..sub.mono", can be represented mathematically as
.SIGMA..sub.mono=m.sub.MHHPSA+m.sub.MNA+m.sub.MTHPA+m.sub.MFD+m.sub.HFDP-
A+m.sub.DMDF
[0065] where
[0066] m.sub.MHHPSA=mass of MHHPSA in grams;
[0067] m.sub.MNA=mass of MNA in grams;
[0068] m.sub.MTHPA=mass of MTHPA in grams;
[0069] m.sub.MFD=mass of MFD in grams;
[0070] m.sub.HFDPA=mass of HFDPA in grams;
[0071] m.sub.DMDF=mass of DMDF in grams.
[0072] Compliance with these preferred mass ratios allows a
user-friendly and storage-stable composition to be obtained. This
is because, in the case of compliance with these mass ratios, the
inventive composition may be processed and used efficiently, since
it does not form dust. On the other hand, the settling of the
heavier particles in the composition may be prevented, as a result
of which no inhomogeneities arise. As is apparent from the
experiments, this is possible in the case of the inventive
composition over a wide range of mass ratios of s-BTDA based on the
sum total of the mass of MHHPSA, MNA, MTHPA, MFD, HFDPA and DMDF in
the composition. Incidentally, it has been observed that a mixture
of the s-BTDA and MTHPA, compared to a mixture of s-BTDA and MNA,
exhibits these advantageous properties over a broad range of
possible mass ratios. This was additionally completely
surprising.
[0073] The amount of BTA used in the inventive composition is not
particularly restricted. In a particularly advantageous embodiment,
the mass of BTA in the composition is 0.01 to 17.6% of the sum
total of the mass of s-BTDA, the mass of MHHPSA, the mass of MNA,
the mass of MTHPA, the mass of MFD, the mass of HFDPA, the mass of
DMDF in the composition. Preferably, the mass of BTA in the
composition is 0.025 to 10% of the sum total of the mass of s-BTDA,
the mass of MHHPSA, the mass of MNA, the mass of MTHPA, the mass of
MFD, the mass of HFDPA, the mass of DMDF in the composition. Even
more preferably, the mass of BTA in the composition is 0.05 to 5%
of the sum total of the mass of s-BTDA, the mass of MHHPSA, the
mass of MNA, the mass of MTHPA, the mass of MFD, the mass of HFDPA,
the mass of DMDF in the composition. Most preferably, the mass of
BTA in the composition is 0.05 to 3% of the sum total of the mass
of s-BTDA, the mass of MHHPSA, the mass of MNA, the mass of MTHPA,
the mass of MFD, the mass of HFDPA, the mass of DMDF in the
composition.
[0074] The expression "sum total of the mass of s-BTDA, the mass of
MHHPSA, the mass of MNA, the mass of MTHPA, the mass of MFD, the
mass of HFDPA, the mass of DMDF", when it is abbreviated
to".SIGMA..sub.mono+s-BTDA", can be represented mathematically
as
.SIGMA..sub.mono+s-BTDA=m.sub.s-BTDA+.SIGMA..sub.mono
[0075] where m.sub.s-BTDA indicates the mass of s-BTDA in grams and
.SIGMA..sub.mono is as defined above.
[0076] The inventive composition may be used particularly in
hardener systems, preferably those for epoxy resins.
[0077] The invention thus relates, in a further aspect, to a
hardener system for epoxy resins, comprising the inventive
composition.
[0078] It will be appreciated that the inventive hardener system,
apart from the s-BTDA, the BTA, the MHHPSA, the MNA, the MTHPA, the
MFD, the HFDPA, the DMDF in the inventive composition, does not
contain any more s-BTDA, BTA, MHHPSA, MNA, MTHPA, MFD, HFDPA,
DMDF.
[0079] The inventive hardener system includes the inventive
composition in a proportion by mass of 0.10-1.0, preferably
0.20-0.999, more preferably 0.40-0.90, most preferably 0.50-0.85,
based in each case on the total mass of the hardener system.
[0080] The inventive hardener system may additionally also include
further additives, for example lubricants, antiblocking agents,
release agents, stabilizers, for example antioxidants, light
stabilizers, heat stabilizers or foam stabilizers, antistats,
conductive additives, flame retardants, pigments, impact modifiers,
flexibilizers, plasticizers, adhesion promoters, fillers, for
example carbon black, calcium carbonate, talc, silicates, cotton
wool, synthetic polymers, metal powders, graphite or glass fibres,
reinforcing materials, blowing agents, kickers, nucleating agents,
antibacterial agents or fungicides. All substances which are known
to those skilled in the art to be suitable additives for production
of epoxy resin systems may be used as the additives mentioned.
[0081] It is a feature of the inventive hardener system that it is
possible to dispense with the use of an amine compound or of a
metal salt as catalyst. It may therefore be preferable that the
inventive hardener system does not include any such catalysts. Of
course, the inventive hardener system may nevertheless also be used
in combination with such a catalyst.
[0082] In the context of the invention, an "amine compound" is
selected from the group consisting of amines, phenolic amines and
cycloaliphatic or aromatic N-heterocycles.
[0083] "Amines" in the context of the invention are
N.sup.1,N.sup.1-dimethylpropane-1,3-diamine (DMAPA),
N.sup.1,N.sup.1,N.sup.3,N.sup.3-tetramethylpropane-1,3-diamine,
N.sup.1,N.sup.1,N.sup.2,N.sup.2-tetramethylethane-1,2-diamine,
N,N-dimethyl-1-benzylamine, N,N-diethyl-1-benzylamine,
triethylamine, tripropylamine, diisopropylethylamine,
2-dimethylaminoethanol or 2-diethylaminoethanol.
[0084] "Cycloaliphatic or aromatic N-heterocycles" in the context
of the invention are pyrrolidine, piperidine, 1-benzylpiperidine,
piperazine, 1,4-dimethylpiperazine, 2,2,6,6-tetramethylpiperidine,
2,2,6,6-tetramethylpiperidine-4-amine,
N-alkyl-2,2,6,6-tetramethylpiperidine-4-amine,
N.sup.1,N.sup.1-dimethyl-N.sup.3-(2,2,6,6-tetramethylpiperidin-4-yl)propa-
ne-1,3-diamine, 2,2,6,6-tetramethylpiperidin-4-ol,
1,2,2,6,6-pentamethylpiperidin-4-ol,
4-alkoxy-2,2,6,6-tetramethylpiperidine,
N.sup.1,N.sup.6-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine,
1H-pyrrole, 1H-imidazole, 1-methyl-1H-imidazole (1MZ),
3-(2-ethyl-4-methyl-1H-imidazol-1-yl)propanenitrile (2E4MZ-CN),
2-ethyl-4-methyl-1H-imidazole (2E4MZ), 2-methyl-1H-imidazole (2MZ),
2-phenyl-1H-imidazole (2PZ), 1-benzyl-2-methyl-1H-imidazole
(1B2MZ), 1-benzyl-2-phenyl-1H-imidazole (1B2PZ),
(4-methyl-2-phenyl-1H-imidazol-5-yl)methanol (2P4MHZ),
(2-phenyl-1H-imidazole-4,5-diyl)dimethanol (2PHZ),
6-(2-(2-methyl-1H-imidazol-1-yl)ethyl)-1,3,5-triazine-2,4-diamine
(2MZ-A), 2,3-dihydro-1H-benzo[d]pyrrolo[1,2-a]imidazole (TBZ),
pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine,
2,6-dimethylpyridine and 1,3-dialkyl-1H-imidazol-3-ium salts,
especially carboxylates, halides, sulphonates, nitrates, sulphates
or hydrogensulphates.
[0085] "Phenolic amines" in the context of the invention are
4-dimethylaminomethylphenol,
2,6-di-tert-butyl-4-dimethylaminomethylphenol (Ionol.RTM. 103),
2,4,6-trisdimethylaminomethylphenol or
2,4-bisdimethylaminomethyl-6-methylphenol.
[0086] "Metal salts" in the context of the invention are zinc(II)
acetylacetonate, (1-methylimidazolium)zinc(II)
acetylacetonate[(1MZ)Zn(acac).sub.2],
bis(1-methylimidazolium)iron(II)
acetylacetonate[(1MZ).sub.2(Fe(acac).sub.2], tin octanoate or boron
trifluoride complexes, especially etherates or complexes with
ethylamine.
[0087] The present invention likewise provides for the use of
hardener systems according to the present invention for hardening
epoxy resin systems. The present invention further provides epoxy
resin systems comprising at least one epoxy resin and at least one
hardener system according to the present invention. The inventive
hardener system has the advantage that it can be incorporated as
such into the epoxy resins, without requiring addition of further
auxiliaries, especially solvents. Preferably, the inventive epoxy
resin system therefore does not contain any solvents. A further
advantage of the present invention lies in the possibility of
achieving hardening below the melting point of s-BTDA and, at the
same time, given selection of suitable hardening cycles, of
arriving at hardened, dimensionally stable systems having a high
glass transition temperature, especially above 200.degree. C.
[0088] In principle, there are no restrictions with regard to the
epoxy resins to be used, meaning that it is also possible for
mixtures of different epoxy resins to be present. Preferably, at
least one epoxy resin having at least 2 epoxy groups per monomer is
present. Said epoxy resin having at least 2 epoxy groups per
monomer can be used alone or in a mixture with further epoxy
resins.
[0089] Especially preferably, no aminic epoxy resins are present in
the inventive epoxy resin system, as described, for example, in EP
0181337 or EP 1091992.
[0090] Examples of suitable epoxy resins include epoxy resins of
the glycidyl ether type, which can be synthesized from bisphenol A
or bisphenol F and epihalohydrins; epoxy resins of the glycidyl
ester type, which can be synthesized from phthalic acid and
epihalohydrins; alicyclic epoxy resins, which can be obtained by
epoxidation from alicyclic dienes such as cyclopentadiene or
cyclohexadiene; epoxidation products of unsaturated polymers, such
as polybutadiene and polyisoprene; and polymers or copolymers of
unsaturated monoepoxides, such as glycidyl methacrylate or allyl
glycidyl ether. This enumeration is merely descriptive. For
example, it is possible to use various polyhydric phenols rather
than bisphenol A, or to use other polybasic acids rather than
phthalic acid.
[0091] The proportion of the hardener system in the mixture with
the epoxy resins is generally calculated from the ratio of the
number of anhydride groups in the hardener system to the number of
epoxy groups in the epoxy resins used. For every mole of epoxy
group present in the epoxy resin used, 0.3-1 mol, more preferably
0.5-0.8 mol, most preferably 0.55-0.75 mol, of anhydride groups is
used.
[0092] In the case of use of the inventive hardener system for
hardening epoxy resins, several embodiments of equal value are
conceivable.
[0093] In one embodiment of the invention, the above-described
hardener system is first produced and then mixed with at least one
epoxy resin. It is preferable in this embodiment that s-BTDA, BTA
and at least one monoanhydride compound selected from the group
consisting of MHHPSA, MNA, MTHPA, MFD, HFDPA, DMDF are present in
the proportions by weight described above.
[0094] A significant advantage of this embodiment is that the user
need merely combine the epoxy resin and the hardener system in the
case of use in the manner of a two-component system. Separate
storage of the individual components of the hardener system is not
required, which leads to simplified applicability.
[0095] In a further embodiment of the present invention, it is
possible at first for only a mixture of the at least one epoxy
resin with s-BTDA and the at least one monoanhydride compound
selected from the group consisting of MHHPSA, MNA, MTHPA, MFD,
HFDPA, DMDF to be present, preferably in the weight ratios
described above, to which the BTA, preferably in the proportions by
weight described above, is subsequently added separately.
[0096] Overall, after addition of the BTA to the epoxy resin
system, the inventive combination of the hardener system is then
likewise present again.
[0097] For this purpose, s-BTDA is first mixed with at least one
monoanhydride compound selected from the group consisting of
MHHPSA, MNA, MTHPA, MFD, HFDPA, DMDF. This mixture is then added to
the at least one epoxy resin. For the actual hardening, BTA is then
added and the hardening is conducted. For the attainment of the
advantage essential to the invention, what is important is merely
that the inventive epoxy resin is present in the course of the
actual hardening of the epoxy resins. The user is thus given the
option of utilizing the advantages of the inventive hardener
system, but at the same time of additionally gaining freedom with
regard to the sequence of addition of the individual
components.
[0098] Thus, methods for hardening epoxy resin systems are likewise
aspects of the invention.
[0099] In a first aspect, this is a method for hardening epoxy
resins, wherein
[0100] a combination of components comprising
5,5'-carbonylbis(isobenzofuran-1,3-dione) and a monoanhydride
compound is added to the epoxy resin to obtain a first resin
mixture;
[0101] 3,3',4,4'-benzophenonetetracarboxylic acid is added to the
first resin mixture to obtain a final epoxy resin mixture; and the
final epoxy resin mixture is hardened at a temperature of at least
25.degree. C.; wherein the monoanhydride compound is selected from
the group consisting of methylhexahydroisobenzofuran-1,3-dione,
5-methyl-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione,
5-methyl-3a,4,7,7a-tetrahydroisobenzofuran-1,3-dione,
3-methylfuran-2,5-dione,
3,3,4,4,5,5-hexafluorodihydro-2H-pyran-2,6(3H)-dione and
3,3-dimethyldihydrofuran-2,5-dione.
[0102] Preferably, the monoanhydride compound in the method of the
first aspect of the invention is selected from the group consisting
of MHHPSA, MTHPA, MNA. More preferably, the monoanhydride compound
is selected from the group consisting of MTHPA, MNA. Most
preferably, the monoanhydride compound is MTHPA.
[0103] In an advantageous embodiment of the method of the first
aspect of the present invention, the ratio of the mass of s-BTDA
used to the sum total of the mass of MHHPSA used, the mass of MNA
used, the mass of MTHPA used, the mass of MFD used, the mass of
HFDPA used, the mass of DMDF used is 1:0.35 to 1:2.05, preferably
1:0.361 to 1:2.010, more preferably 1:0.619 to 1:1.237.
[0104] In a particularly advantageous embodiment of the method of
the first aspect of the invention, the mass of BTA used in the
method is 0.01% to 17.6% of the sum of the mass of s-BTDA used, the
mass of MHHPSA used, the mass of MNA used, the mass of MTHPA used,
the mass of MFD used, the mass of HFDPA used, the mass of DMDF
used.
[0105] In a preferred embodiment of the method of the first aspect
of the invention, the mass of BTA used in the method is 0.025% to
10% of the sum of the mass of s-BTDA used, the mass of MHHPSA used,
the mass of MNA used, the mass of MTHPA used, the mass of MFD used,
the mass of HFDPA used, the mass of DMDF used.
[0106] In a more preferred embodiment of the method of the first
aspect of the invention, the mass of BTA used in the method is
0.05% to 5% of the sum of the mass of s-BTDA used, the mass of
MHHPSA used, the mass of MNA used, the mass of MTHPA used, the mass
of MFD used, the mass of HFDPA used, the mass of DMDF used.
[0107] In an even more preferred embodiment of the method of the
first aspect of the invention, the mass of BTA used in the method
is 0.05% to 3% of the sum of the mass of s-BTDA used, the mass of
MHHPSA used, the mass of MNA used, the mass of MTHPA used, the mass
of MFD used, the mass of HFDPA used, the mass of DMDF used.
[0108] In a method of a second aspect, a hardener mixture
comprising 5,5'-carbonylbis(isobenzofuran-1,3-dione),
3,3',4,4'-benzophenonetetracarboxylic acid and a monoanhydride
compound is prepared, an epoxy resin is added to the hardener
mixture to obtain an epoxy resin hardener mixture; and the epoxy
resin hardener mixture is hardened at a temperature of at least
25.degree. C., wherein the monoanhydride compound is selected from
the group consisting of methylhexahydroisobenzofuran-1,3-dione,
5-methyl-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione,
5-methyl-3a,4,7,7a-tetrahydroisobenzofuran-1,3-dione,
3-methylfuran-2,5-dione,
3,3,4,4,5,5-hexafluorodihydro-2H-pyran-2,6(3H)-dione and
3,3-dimethyldihydrofuran-2,5-dione.
[0109] Preferably, the monoanhydride compound in the method of the
second aspect is selected from the group consisting of MHHPSA,
MTHPA, MNA. More preferably, the monoanhydride compound in the
method of the second aspect of the invention is selected from the
group consisting of MTHPA, MNA. Most preferably, the monoanhydride
compound in the method of the second aspect of the invention is
MTHPA.
[0110] In an advantageous embodiment of the method of the second
aspect of the present invention, the ratio of the mass of s-BTDA
used to the sum total of the mass of MHHPSA used, the mass of MNA
used, the mass of MTHPA used, the mass of MFD used, the mass of
HFDPA used, the mass of DMDF used is 1:0.35 to 1:2.05, preferably
1:0.361 to 1:2.010, more preferably 1:0.619 to 1:1.237.
[0111] In a particularly advantageous embodiment of the method of
the second aspect of the invention, the mass of BTA used in the
method is 0.01% to 17.6% of the sum of the mass of s-BTDA used, the
mass of MHHPSA used, the mass of MNA used, the mass of MTHPA used,
the mass of MFD used, the mass of HFDPA used, the mass of DMDF
used.
[0112] In a preferred embodiment of the method of the second aspect
of the invention, the mass of BTA used in the method is 0.025% to
10% of the sum of the mass of s-BTDA used, the mass of MHHPSA used,
the mass of MNA used, the mass of MTHPA used, the mass of MFD used,
the mass of HFDPA used, the mass of DMDF used.
[0113] In a more preferred embodiment of the method of the second
aspect of the invention, the mass of BTA used in the method is
0.05% to 5% of the sum of the mass of s-BTDA used, the mass of
MHHPSA used, the mass of MNA used, the mass of MTHPA used, the mass
of MFD used, the mass of HFDPA used, the mass of DMDF used.
[0114] In an even more preferred embodiment of the method of the
second aspect of the invention, the mass of BTA used in the method
is 0.05% to 3% of the sum of the mass of s-BTDA used, the mass of
MHHPSA used, the mass of MNA used, the mass of MTHPA used, the mass
of MFD used, the mass of HFDPA used, the mass of DMDF used.
[0115] In the method according to the invention for hardening epoxy
resin systems according to the first and second aspects above, the
hardening may be effected at a temperature of at least 25.degree.
C., especially at a temperature of at least 50.degree. C. The
hardening may be effected, for instance, at a temperature in the
range from 25.degree. C. to below the melting temperature of the
s-BTDA, especially at a temperature in the range from 25.degree. C.
to 200.degree. C., preferably at a temperature in the range from
25.degree. C. to 180.degree. C. The melting temperature of the
s-BTDA is in the range from 230.degree. C. to 250.degree. C.
[0116] The present invention is illustrated by the examples which
follow, without being restricted thereto.
EXAMPLES
1. Examples 1-10
Determination of the Gel Time at 170.degree. C. to DIN EN 16 945,
Sheet 1
[0117] In a 100 ml beaker, at room temperature, s-BTDA, BTA and
MTHPA (Comparative Example 1 and Inventive Examples 2-5) or MNA
(Comparative Example 6 and Inventive Examples 7-10) were mixed with
one another according to the values specified in Table 1.
Subsequently, a wooden spatula was used to incorporate 10 g of the
cycloaliphatic epoxy resin CY179 having the following structural
formula:
##STR00002##
[0118] so as to form a homogeneous composition.
[0119] 10 g of the mixture thus obtained were transferred into a
test tube, then the gel time at 170.degree. C. was determined to
DIN EN 16945, Sheet 1. Table 1 shows the respective gel times
obtained. The left-hand column indicates the number of the
particular example.
TABLE-US-00001 TABLE 1 Proportion in the Gel time MTHPA MNA s-BTDA
BTA hardener at 170.degree. C. [g] [g] [g] [g] [%] [min] 1 10.0 0
10.0 0.0 0.0 36.85 2 10.0 0 9.5 0.5 2.6 16.00 3 10.0 0 9.0 1.0 5.3
12.08 4 10.0 0 8.0 2.0 11.1 14.08 5 10.0 0 7.0 3.0 17.6 12.91 6 0
10.0 10.0 0.0 0.0 60.92 7 0 10.0 9.5 0.5 2.6 52.00 8 0 10.0 9.0 1.0
5.3 38.83 9 0 10.0 8.0 2.0 11.1 23.25 10 0 10.0 7.0 3.0 17.6
17.42
[0120] As shown in Table 1, a distinct reduction in the gel time
was observed in the case of very small proportions of BTA in the
mixture. This was attributable to the accelerating and completely
surprising property of the BTA.
2. Examples 11-32
(Inventive) Formulation
[0121] A 100 ml beaker was initially charged with 9.7 g of s-BTDA
and 0.3 g of BTA. Thereafter, MTHPA or MNA was added stepwise in
accordance with the amounts shown in Table 2 and the mixture was
stirred at 23.degree. C. for about one minute to give a homogeneous
composition. Thereafter, the consistency was checked visually.
Table 2 below indicates, in the penultimate column, the consistency
of the mixture obtained in the case that the monoanhydride compound
used was MTHPA ("MTHPA" column) and, in the last column, the
consistency in the case that the monoanhydride compound used was
MNA ("MNA" column). "Free-flowing" means that no paste was
obtained; instead, the mixture was in pulverulent form. "Pasty"
means that the homogeneous mixture was of spreadable consistency
and remained homogeneous even over a long period, i.e. more than
one hour, without the suspended solids content consisting of BTA
and s-BTDA settling out. "Unstable" means that the mixture obtained
was at first homogeneous but the suspended solids content
consisting of BTA and s-BTDA settled out after less than one hour.
The left-hand column in Table 2 indicates the number of the
particular example. One example consists of two experiments in each
case, with use of the appropriate amount of MTHPA in the first and
of the appropriate amount of MNA in the second as the monoanhydride
compound.
[0122] It is apparent from Table 2 that, in the case that MTHPA as
the monoanhydride was used in combination with s-BTDA, an
advantageous pasty structure was the result over a very broad
mixing range. Thus, the disadvantageous free-flowing consistency
was not found until a mixing ratio of s-BTDA:MTHPA of 1:0.309 or
for even smaller proportions of MTHPA, while instability was not
detected until a proportion of 1:2.062 or for even higher
proportions of MTHPA. The corresponding range of values for MNA is
much narrower: Thus, the disadvantageous free-flowing consistency
was still found at a mixing ratio of s-BTDA:MNA of 1:0.515 or for
even smaller proportions of MNA, while instability was already
detected at a proportion of 1:1.340 or for even higher proportions
of MNA. This broad range in which MTHPA could be mixed with s-BTDA
and results in a structure of good processibility was completely
surprising compared to the results in the case of the combination
of s-BTDA and MNA.
TABLE-US-00002 TABLE 2 Mixing ratio BTA s-BTDA Monoanhydride Mono-
[g] [g] [g] s-BTDA anhydride MTHPA MNA 11 0.3 9.7 1.0 1.000 0.103
free-flowing free-flowing 12 0.3 9.7 2.0 1.000 0.206 free-flowing
free-flowing 13 0.3 9.7 3.0 1.000 0.309 free-flowing free-flowing
14 0.3 9.7 3.5 1.000 0.361 pasty free-flowing 15 0.3 9.7 4.0 1.000
0.412 pasty free-flowing 16 0.3 9.7 5.0 1.000 0.515 pasty
free-flowing 17 0.3 9.7 6.0 1.000 0.619 pasty pasty 18 0.3 9.7 7.0
1.000 0.722 pasty pasty 19 0.3 9.7 8.0 1.000 0.825 pasty pasty 20
0.3 9.7 9.0 1.000 0.928 pasty pasty 21 0.3 9.7 10.0 1.000 1.031
pasty pasty 22 0.3 9.7 11.0 1.000 1.134 pasty pasty 23 0.3 9.7 12.0
1.000 1.237 pasty pasty 24 0.3 9.7 13.0 1.000 1.340 pasty unstable
25 0.3 9.7 14.0 1.000 1.443 pasty unstable 26 0.3 9.7 15.0 1.000
1.546 pasty unstable 27 0.3 9.7 16.0 1.000 1.649 pasty unstable 28
0.3 9.7 17.0 1.000 1.753 pasty unstable 29 0.3 9.7 18.0 1.000 1.856
pasty unstable 30 0.3 9.7 19.0 1.000 1.959 pasty unstable 31 0.3
9.7 19.5 1.000 2.010 pasty unstable 32 0.3 9.7 20.0 1.000 2.062
unstable unstable
[0123] The above description is presented to enable a person
skilled in the art to make and use the invention, and is provided
in the context of a particular application and its requirements.
Various modifications to the preferred embodiments will be readily
apparent to those skilled in the art, and the generic principles
defined herein may be applied to other embodiments and applications
without departing from the spirit and scope of the invention. Thus,
this invention is not intended to be limited to the embodiments
shown, but is to be accorded the widest scope consistent with the
principles and features disclosed herein. In this regard, certain
embodiments within the invention may not show every benefit of the
invention, considered broadly.
* * * * *